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  • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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  • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
  • C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
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  • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
  • H10K85/146—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE poly N-vinylcarbazol; Derivatives thereof
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  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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Definitions

• the present invention relates to a polymer for an organic electroluminescent device having a structure in which an indolocarbazole unit is contained in a side chain, and an organic electroluminescent device using the same.
• electroluminescent elements include inorganic electroluminescent elements using inorganic compounds and organic electroluminescent elements using organic compounds.
• organic light emitting devices with low voltage and high luminance can be obtained. Research on practical application of electroluminescent devices is actively conducted.
• the structure of the organic electroluminescence device is that a hole injection layer is formed on a glass plate on which a thin film of an anode material such as indium-tin oxide (ITO) is deposited, and an organic thin film layer such as a light emitting layer is further formed thereon.
• a device is formed by forming a thin film of a cathode material, and there is an element in which a hole transport layer and an electron transport layer are appropriately provided in this basic structure.
• the layer structure of the organic electroluminescent device is, for example, anode / hole injection layer / light emitting layer / electron transport layer / cathode, anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode, etc. is there.
• Hole transport materials used for the hole transport layer of the organic electroluminescence device are roughly classified into low molecular weight hole transport materials and high molecular weight hole transport materials.
• a vacuum deposition method is mainly used.
• various materials having different functions can be easily multilayered.
• high-performance organic electroluminescent elements can be formed, it is difficult to uniformly control the film thickness and paint separately due to the large screen and high definition of the panel. There is a problem of becoming higher.
• a solution coating method such as a spin coating method, a printing method, an ink jet method or the like is used.
• This method is easy to enlarge the screen and is excellent in mass production, but has a problem that it is difficult to laminate the coating film and impurities are easily mixed therein. Therefore, an element using a high molecular weight hole transport material is inferior in element performance such as element efficiency and lifetime as compared with a low molecular weight hole transport material. Accordingly, there has been a demand for a polymer-based hole transport material having both excellent hole transport performance and good film forming properties.
• Non-Patent Document 1 is linked with polyvinylcarbazole and polysilane
• Patent Document 2 and Non-Patent Document 2 are linked with vinyltriphenylamine and triphenylamine with methylene. Structured polymers have been reported. However, organic electroluminescence devices using these have poor luminous efficiency and device stability, and have not been sufficiently improved.
• Patent Document 3 discloses a conjugated polymer bonded at the peripheral position of indolocarbazole
• Patent Document 4 discloses a conjugated polymer in which an indolocarbazole unit is introduced into a polyarylene main chain.
• these polymers have improved charge mobility, ⁇ -conjugated polymers containing an indolocarbazole skeleton in the main chain have extremely low solubility in organic solvents and are not suitable for film formation by the solution coating method. is there.
• Patent Document 5 discloses a polymer material in which a specific indole trimer site is incorporated into a polymer side chain, but the stability of the device is poor, and sufficient improvement has not been achieved.
• soot polymer In order to apply the soot polymer to an organic electroluminescence device, it is necessary to improve the charge transport ability, and to improve the stability of the film, the solubility in a solvent and the film forming property.
• This invention is made
• Another object of the present invention is to provide an organic electroluminescent element using the polymer used for a lighting device, an image display device, a backlight for a display device, and the like.
• the present invention relates to a polymer for an organic electroluminescent device comprising an indolocarbazole skeleton, or an indolocarbazole skeleton and a charge transporting skeleton in a polymer side chain, and an anode layer laminated on a substrate,
• the present invention relates to an organic electroluminescent device having an organic layer between cathode layers, wherein at least one of the organic layers is a layer containing the polymer.
• the present invention relates to a polymer for an organic electroluminescence device characterized by having a repeating unit represented by the following general formula (1) in a repeating unit constituting a main chain.
• R is a hydrogen atom, C 1 -C 20 alkyl group, C 1 -C 20 alkoxy group, C 6 -C 30 aryl group, C 6 -C 30 aryloxy group, C 7 -C 36
• Y is a single bond, a C 1 -C 20 alkylene group, a C 6 -C 30 arylene group, a C 3 -C 30 heteroarylene group, CO, COO, or O.
• Z is an N-substituted indolocarbazolyl group and W is a charge transporting group, but is not the same as Z.
• m and n represent the molar ratio, and m is 0 to 95 mol% and n is 5 to 100 mol%, assuming that all repeating units are 100 mol%.
• l represents the average number of repetitions and is 2 to 10,000.
• m is preferably 0 mol%, or in general formula (1), m is preferably 5 to 95 mol%, and n is preferably 5 to 95 mol%.
• the weight average molecular weight of the polymer for organic electroluminescent elements is preferably 1,000 to 1,000,000.
• Z in the general formula (1) includes one or more selected from indolocarbazolyl groups represented by the following formulas (2) to (7).
• each X is independently C—H, N or CL
• L is independently a C 6 -C 30 aryl group, C 3 -C 30 hetero Represents an aryl group or a C 12 -C 60 diarylamino group
• R 1 is independently a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 30 aryl group, a C 6 -C 30 aryloxy group, or a C 7 -C 36 aryl group.
• Examples of W in the general formula (1) include a charge transporting group represented by the following formula (8) or (9).
• X 2 is each independently any one of C—H, N, O, S or C—L
• L is independently a C 6 -C 30 aryl group, C 3 heteroaryl group ⁇ C 30, or a diarylamino group having C 12 ⁇ C 60, may form a fused ring bound to the ring comprising X 2.
• Examples of W in the general formula (1) include charge transporting groups represented by the following formula (10) or (11).
• R 2 is a hydrogen atom, a C 1 to C 20 alkyl group, a C 1 to C 20 alkoxy group, a C 6 to C 30 aryl group, or a C 6 to C 30 aryl group.
• the present invention is an organic electroluminescent device having an organic layer between an anode layer and a cathode layer laminated on a substrate, wherein the organic layer contains the polymer for an organic electroluminescent device in at least one layer of the organic layer.
• the present invention relates to an organic electroluminescent device characterized by the following.
• a hole transport layer is mentioned as an organic layer containing the said polymer for organic electroluminescent elements.
• the present invention relates to a polymer for an organic electroluminescence device, which is represented by the following general formula (12), and has an indolocarbazole skeleton as a pendant in a repeating unit constituting a main chain.
• R, Y and Z are the same as those in the general formula (1).
• p is the same as 1 in the general formula (1).
• the present invention is an organic compound represented by the general formula (1), wherein the repeating unit constituting the main chain has an indolocarbazole skeleton as a pendant, and has a weight average molecular weight of 1,000 to 1,000,000.
• the present invention relates to a polymer for an electroluminescent element.
• m and n represent the molar ratio, and m is 5 to 95 mol% and n is 5 to 95 mol%, assuming that all repeating units are 100 mol%.
• l represents the number of repetitions.
• the polymer for organic electroluminescent elements of the present invention is an oligomer or a polymer represented by the general formula (1).
• the polymer for organic electroluminescent elements of the present invention can be a homopolymer or a copolymer.
• General formula (12) corresponds to the case where m is 0 in General formula (1), and R, Y, and Z in General formula (12) are the same as General formula (1), Since p corresponds to l, the meaning of these symbols can be understood from the description of the general formula (1). Since the description related to the general formula (1) is common to the general formula (12), it is represented by the description related to the general formula (1).
• Z and W are pendants (side chains), Z is a group having an indolocarbazole skeleton bonded at the N position, and W is a charge transporting group. If the unit containing Z is Uz and the unit containing W is Uw, the general formula (1) can be expressed as the following formula (1A). [(Uw) m- (Uz) n ] l (1A)
• the polymer for an organic electroluminescence device of the present invention has an indolocarbazole skeleton capable of imparting excellent charge transporting ability, particularly hole transporting ability, as a pendant (side chain) in a unit constituting the main chain.
• the unit which comprises a principal chain means a repeating unit, this repeating unit may be not only 1 type but 2 or more types.
• l and p are the number of repetitions and are determined by the weight average molecular weight, but the average (number average) number of repetitions is 2 to 10,000, preferably 5 to 1,000. .
• the polymer for an organic electroluminescent element of the present invention may contain a unit other than the repeating unit represented by the general formula (1) or a terminal, but the repeating unit represented by the general formula (1) is all repeating units. It is 50 mol% or more, preferably 80 mol% or more.
• R is a hydrogen atom, a C 1 to C 20 alkyl group, a C 1 to C 20 alkoxy group, a C 6 to C 30 aryl group, a C 6 to C 30 aryloxy group, C arylalkyl group 7 ⁇ C 36, arylalkyloxy group of C 7 ⁇ C 36, C 3 heteroaryl group ⁇ C 30, C 3 heteroaryloxy group ⁇ C 30, or C 3 to ⁇ C 30 cycloalkyl Groups, which may be the same or different.
• these groups contain a hydrocarbon chain, it may be a straight chain or a branched chain, and may be substituted with a halogen such as Cl or F.
• a hydrogen atom a C 1 -C 12 alkyl group, a C 1 -C 12 alkoxy group, a C 6 -C 24 aryl group, a C 6 -C 24 aryloxy group, a C 7 -C 28 aryl group
• each of the unit Uz containing Z and the unit Uw containing W three Rs are present, and it is preferable that two or three of them are hydrogen atoms, and that three of them are hydrogen atoms. More preferred.
• these groups may have a substituent, and in the case of having a substituent, the carbon number is calculated including the substituent.
• the substituent is not particularly limited as long as it does not inhibit the performance, but is preferably a C 1 to C 4 alkyl group, a phenyl group, a pyridyl group, or a carbazolyl group.
• Y is a single bond, a C 1 -C 20 alkylene group, a C 6 -C 30 arylene group, a C 3 -C 30 heteroarylene group, CO, COO or O, preferably a single bond, C 6 A C 30 -arylene group and a C 3 -C 30 heteroarylene group.
• these groups may contain a hydrocarbon chain, it may be a straight chain or a branched chain, and may be substituted with a halogen such as Cl or F.
• these groups may have a substituent and are the same as the substituent demonstrated by said R.
• Y is more preferably a single bond because the longer the linking group, the lower the charge transport capability in the repeating unit and the thermal instability.
• Z is an indolocarbazolyl group bonded at the N position.
• This indolocarbazolyl group is a group formed by taking one H from a compound having a substituent at one N-position of a five-ring condensed ring compound in which an indole ring and a carbazole ring are condensed.
• This indolocarbazolyl group has two Ns, but one N is bonded to a substituent and the other N is bonded to the main chain via Y. It is good that it is.
• the indolocarbazolyl group bonded at the N-position is also referred to as an N-indolocarbazolyl group, and can have a substituent on the carbon constituting the indolocarbazole ring.
• this indolocarbazolyl group has a plurality of condensable positions of the indole ring and the carbazole ring, it can take groups of six structural isomers of the following formulas (A) to (F).
• Structural isomers of The indolocarbazolyl group preferably has a 6-membered aromatic group at the other N-position not bonded to the main chain.
• the indolocarbazole group (including the 6-membered aromatic group substituted at the other N-position) can have a substituent as long as the effects of the present invention are not impaired.
• the N-indolocarbazolyl group represented by Z in the general formula (1) is any one or two selected from the group consisting of the structures shown in the above formulas (2) to (7) The above indolocarbazolyl group.
• Z in the general formula (1) is composed of two or more kinds of indolocarbazolyl groups.
• R 1 is independently a C 1 to C 20 alkyl group, a C 1 to C 20 alkoxy group, a C 6 to C 30 aryl group, a C 6 to C 30 An aryloxy group, a C 7 -C 36 arylalkyl group, a C 7 -C 36 arylalkyloxy group, a C 3 -C 30 heteroaryl group, a C 3 -C 30 heteroaryloxy group, or a C 3- C 30 cycloalkyl group, preferably C 1 -C 20 alkyl group, C 6 -C 30 aryl group, C 7 -C 36 arylalkyl group, C 3 -C 30 heteroaryl group .
• these groups may contain a hydrocarbon chain, it may be a straight chain or a branched chain, and may be substituted with a halogen such as Cl or F.
• These groups may further have a substituent, and are the same as the substituents described for R in the general formula (1).
• each X is independently CH, N, or CL.
• L is an aryl group of C 6 ⁇ C 30 is independently diarylamino groups C 3 heteroaryl group ⁇ C 30, or C 12 ⁇ C 60, aryl group of C 6 ⁇ C 24, C 3 It is preferably a -C 24 heteroaryl group or a C 12 -C 36 diarylamino group.
• preferred aryl group, heteroaryl group, or aryl group of diarylamino group include benzene, pentalene, indene, naphthalene, azulene, heptalene, octalene, indacene, acenaphthylene, phenalene, phenanthrene, anthracene, tridene, fluoranthene, aceto Phenanthrylene, aseantrilene, triphenylene, pyrene, chrysene, tetraphen, tetracene, pleiaden, picene, perylene, pentaphen, pentacene, tetraphenylene, cholanthrylene, helicene, hexaphene, rubicene, coronene, trinaphthylene, heptaphene, pyranthrene, overene , Coranulene, fluorene, an
• benzene More preferred are benzene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, indole, carbazole, or a group formed by removing hydrogen from an aromatic compound in which a plurality of these aromatic rings are connected, and a diphenylamino group.
• the aromatic ring is a group derived from a linked aromatic compound, the number to be linked is preferably 2 to 10, more preferably 2 to 5, and the linked aromatic rings may be the same. It may be different.
• the aryl group of the aryl group, heteroaryl group, or diarylamino group may have a substituent, and when it has a substituent, the total number of substituents is 1 to 10, preferably 1 to 6. Yes, more preferably 1 to 4.
• the group which arises from the aromatic compound with which multiple aromatic rings were connected can also have a substituent.
• the substituent is not limited, but preferred substituents include alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 20 carbon atoms.
• Examples include a substituted amino group, an acyl group having 2 to 20 carbon atoms, and a diarylamino group having 12 to 24 carbon atoms. More preferably, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, phenyl group, pyridyl group , Diphenylamino group and carbazolyl group. When it has two or more substituents, they may be the same or different.
• m and n represent a molar ratio, and when the total repeating unit is 100 mol%, m is 5 to 95 mol% and n is 5 to 95 mol%.
• m is preferably 10 to 90 mol%, more preferably 50 to 80 mol%.
• n is preferably 10 to 90 mol%, more preferably 20 to 50 mol%.
• l represents the number of repetitions and is determined by the weight average molecular weight, and the average (number average) number of repetitions is 2 to 10,000, preferably 5 to 1,000.
• the W W in the general formula (1) is a charge transporting group.
• the charge transporting group includes a hole transporting group and an electron transporting group.
• the hole transporting group is mainly responsible for the transport of holes, so stability to holes, that is, oxidation stability is required.
• the electron transporting group is responsible for transport of electrons, so that stability to electrons, that is, reduction stability. Sex is required.
• the mobility for each charge that is, the hole mobility in the case of a hole transporting group, and the electron mobility in the case of an electron transporting group is higher from an adjacent layer such as a hole injection layer. It is more preferable because the generated charge can be efficiently taken into the light emitting layer and the driving voltage of the element can be lowered.
• a group containing a unit such as carbazole or phenylamine can be used, and as the electron transporting group, a group containing an oxadiazole unit, a triazine unit, a triazole unit or the like can be used.
• W is not the same as Z, so W is not an N-substituted indolocarbazolyl group.
• any one of the charge transporting groups represented by the above formulas (8) to (9) and formulas (10) to (11) is preferably mentioned.
• X 2 is each independently any of C—H, N, O, S, or C—L
• L is independently a C 6 to C 30 aryl group, C 3 heteroaryl group ⁇ C 30, or a diarylamino group having C 12 ⁇ C 60, may form a fused ring bound to the ring comprising X 2.
• These groups may further have a substituent, and are the same as the substituents described for X in the general formulas (2) to (7).
• R 2 is a hydrogen atom, a C 1 to C 20 alkyl group, a C 1 to C 20 alkoxy group, a C 6 to C 30 aryl group, or a C 6 to C 30 aryl.
• these groups contain a hydrocarbon chain, it may be linear or branched. Further, these groups may further have a substituent, and are the same as the substituents described for R in the general formula (1).
• the repeating unit forming the main chain is not particularly limited, but indolocarbazolyl group or charge transport property from the viewpoint of ease of polymerization and improvement of device performance.
• a polymer having a repeating unit of an ethylene chain or a styrene chain obtained by polymerizing or copolymerizing a vinyl compound substituted with a group is preferable.
• vinyl compound that gives a unit having an N-indolocarbazolyl group or Uz
• vinyl compounds may be used alone or in combination of two or more as required. Moreover, it is not limited to the illustrated compound.
• a vinyl compound that gives a unit having a charge transporting group or Uw is exemplified below.
• the vinyl compound substituted with a charge transporting group includes a vinyl compound substituted with a hole transporting group, a vinyl compound substituted with an electron transporting group, or a vinyl compound substituted with both transporting groups. These vinyl compounds may be used alone or in combination of two or more as required. Also, it is not limited to the exemplified compounds
• the polymer for indolocarbazole-based organic electroluminescence device of the present invention can be easily produced by polymerizing monomers by a known method. For example, it can be produced by the following reaction formula.
• the polymerization method may be any of radical polymerization, anionic polymerization, cationic polymerization, and addition polymerization, but radical polymerization is desirable from a general viewpoint.
• the above is a production example of a polymer obtained by polymerizing a single monomer, but a production example of a polymer obtained by copolymerizing a plurality of monomers is a monomer having a charge transporting group in the same manner as described above. Is shown, and this is copolymerized with the above monomers.
• the weight average molecular weight Mw of the indolocarbazole-based polymer of the present invention is 1,000 to 1,000,000, preferably 5,000 to 300,000. If Mw is less than 1,000, it is difficult to form a uniform film, and if it exceeds 1,000,000, the solubility in organic solvents becomes extremely poor, and solution coating becomes difficult.
• polymers having an indolocarbazole skeleton of the present invention are shown below, but are not limited thereto.
• the polymer for organic electroluminescent elements of the present invention may contain a small amount of other repeating units as long as the effects of the present invention are not impaired.
• a small amount of units derived from methacrylic acid ester or styrene may be present.
• the polymerization type may be random or block.
• the copolymers of the formulas p-11 to p-12 are alternately polymerized, but may be random or block.
• the polymer for organic electroluminescent elements of the present invention gives an excellent organic electroluminescent element by being contained in the organic layer of the organic EL element.
• at least one organic layer selected from a light emitting layer, a hole transport layer, an electron transport layer, and a hole blocking element layer may be contained. More preferably, it may be contained as a material for the hole transport layer.
• the polymer for organic electroluminescent elements of the present invention is also referred to as the polymer of the present invention.
• the organic electroluminescent device using the polymer of the present invention has a plurality of organic layers between a pair of anode and cathode, and in particular, a hole transport layer / light emitting layer / electron transport layer, a hole transport layer / light emitting layer / It is preferably composed of an electron transport layer or a hole transport layer / light emitting layer / electron transport layer. Particularly preferred is a layer structure of hole transport layer / light emitting layer / electron transport layer.
• the organic electroluminescent element of this invention can also provide a protective layer in each after forming each organic layer. Furthermore, a protective film may be provided to protect the entire element from moisture and oxygen.
• the light emitting layer is a layer containing a light emitting material and may be fluorescent or phosphorescent. Alternatively, a light emitting material may be used as a dopant and a host material may be used in combination. As the light emitting material in the light emitting layer, the following compounds can be used as the fluorescent light emitting material.
• the phosphorescent material preferably contains an organometallic complex containing at least one metal selected from ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum and gold.
• organometallic complexes are known in the above-mentioned patent documents and the like, and these can be selected and used.
• Phosphorescent materials for obtaining high luminous efficiency include complexes such as Ir (ppy) 3 having a noble metal element such as Ir as a central metal, complexes such as Ir (bt) 2 ⁇ acac 3 , and PtOEt 3 Complexes are mentioned. Specific examples of phosphorescent light emitting materials are shown below, but are not limited thereto.
• an organic electroluminescent device having various emission wavelengths can be obtained.
• the amount contained in the light emitting layer is preferably in the range of 1 to 50% by weight. More preferably, it is 5 to 30% by weight.
• the host material in the light emitting layer a known host material can be used, and the polymer of the present invention can also be used as the host material. Moreover, you may use the polymer of this invention, and another host material together.
• a known host compound that can be used is preferably a compound that has a hole transporting ability and an electron transporting ability, prevents a long wavelength of light emission, and has a high glass transition temperature.
• host materials are known from a large number of patent documents and can be selected from them.
• Specific examples of the host material are not particularly limited, but include indole derivatives, carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine.
• arylamine derivatives amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, anthraquino Heterocyclic tetracarboxylic acid anhydrides such as dimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene,
• metal complexes typified by metal complexes of Russianine derivatives, 8-quinolinol derivatives, metal phthalocyanines, metal complexes of benzoxazole and benzothiazole derivatives, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline copolymers, Examples thereof include polymer compounds such
• the hole transporting compound for forming the positive hole transporting layer the polymer for organic electroluminescence device of the present invention is advantageously used. If necessary, a tertiary amine triphenylamine derivative, carbazole derivative and the like are exemplified as long as the object of the present invention is not impaired.
• One or more low molecular hole transporting compounds may be blended as an additive and used as a composition. Specific examples of the hole transporting compound are shown below, but are not limited thereto.
• Examples of the electron transport compound that forms the electron transport layer include oxadiazole derivatives, imidazole derivatives, and triazole derivatives. If necessary, one or two or more low molecular electron transport compounds may be blended as additives and used as a composition within a range not impairing the object of the present invention. Specific examples of the electron transporting compound are shown below, but are not limited thereto.
• a hole injection layer may be inserted between the anode and the hole transport layer or the light emitting layer.
• a hole injection material for forming the hole injection layer conductive polymers such as polythiophene derivatives and polypyrrole derivatives can be used. Of these, poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS), which is a polythiophene derivative, is preferable from the viewpoint of hole injection efficiency.
• the thickness is preferably 200 nm or less, more preferably 100 nm or less.
• the soot anode supplies holes to a hole injection layer, a hole transport layer, a light emitting layer or the like, and is generally formed on a glass substrate.
• the anode material used in the present invention is not particularly limited, and specific examples include conductive metal oxides such as indium-tin oxide (ITO) and tin oxide, and metals such as gold, silver, and platinum.
• ITO indium-tin oxide
• tin oxide such as gold, silver, and platinum.
• Commercially available glass with ITO can also be used.
• Commercially available glass with ITO is usually used after cleaning with a cleaning agent aqueous solution and a solvent, and then cleaning with a UV ozone irradiation device or a plasma irradiation device.
• the cathode supplies electrons to the electron transport layer or the light emitting layer
• the anode material used in the present invention is not particularly limited.
• metals such as Li, Mg, Ca, Al and alloys thereof,
• Mg—Ag alloy, Mg—Al alloy and the like can be mentioned.
• the cathode and anode can be formed by a known method, that is, vacuum deposition or sputtering.
• the thickness of the cathode is preferably 300 nm or less, more preferably 200 nm or less, while the thickness of the anode is preferably 200 nm or less, more preferably 100 nm or less.
• a spin coating method is generally used as a method for forming a polymer layer such as a polymer light-emitting material, a polymer material for a hole transport layer, or a polymer material for an electron transport layer.
• a spin coating method is generally used as a method for forming a polymer layer such as a polymer light-emitting material, a polymer material for a hole transport layer, or a polymer material for an electron transport layer.
• examples of the method for forming the organic polymer layer include, but are not limited to, an inkjet method, a printing method, a spray coating method, and a dispenser method.
• the compounds synthesized in the examples were identified by one or more analytical methods selected from 1 H-NMR (solvent: deuterated chloroform), FD-MS, GPC, TGA, DSC, UV and IR analysis.
• Example 1 Compound (A-2) is synthesized from compound (A-1) according to scheme (13), and then polymer (P-1) is synthesized.
• the resulting compound (A-2) was polymerized to synthesize a polymer (P-1). Specifically, 0.5 g (0.17 mmol) of the compound (A-2) was dissolved in 25 ml of benzene, 0.27 g of AIBN was added as a catalyst, and the reaction was carried out at 70 ° C. for 17 hours after substitution with nitrogen. The reaction solution was diluted and purified by reprecipitation using acetonitrile. The purified polymer content was recovered, and this was again put into acetonitrile and repeatedly reslurried to obtain 0.10 g of polymer (P-1). The resulting polymer was identified by GPC, TGA and DSC. Mw was 6,000 in terms of polystyrene of GPC (THF), and the molecular weight distribution was 2.0. Moreover, Tg calculated
• Example 2 The device of the polymer (P-1) obtained in Example 1 was evaluated. First, a glass substrate with ITO having a film thickness of 150 nm subjected to solvent washing and UV ozone treatment, and poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS) as a hole injection layer: (H.C.) -Stark Co., Ltd. product name: Clevios PCH8000) was formed to a film thickness of 25 nm. Next, the synthesized polymer (P-1) was dissolved in THF to prepare a 0.4 wt% solution, and a film having a thickness of 20 nm was formed as a hole transport layer by spin coating.
• PEDOT / PSS polystyrene sulfonic acid
• the organic electroluminescence device When an external power source was connected to the organic electroluminescence device thus obtained and a DC voltage of 0 to 10 V was applied, it was confirmed that the organic EL device had the light emission characteristics as shown in Table 1 at a current density of 20 mA / cm 2 .
• the maximum wavelength of the device emission spectrum was 550 nm, and green emission derived from an iridium complex was observed.
• Example 3 When polymerizing compound (A-2), polymer (P-2) was obtained in the same manner as in Example 1, except that the amount of AIBN as an initiator was changed to 0.12 g and the amount of benzene in the solvent was changed to 15 ml. It was.
• the polymer had an Mw of 20,000 and a molecular weight distribution of 2.2.
• the Tg of the polymer was 214 ° C.
• the element evaluation was performed in the same manner as in Example 2.
• Example 4 Compound (A-3) is synthesized from compound (A-1) according to scheme (14), and then polymer (P-3) is synthesized.
• the compound (A-3) 0.30 g obtained, dehydrated THF 30 ml, and AIBN 5.6 mg as a catalyst were charged and polymerized at 60 ° C. for 48 hours.
• the polymerization solution was purified by reprecipitation using acetone to obtain 0.11 g of polymer (P-3).
• the polymer had an Mw of 17,000 and a molecular weight distribution of 2.6.
• the Tg of the polymer was 217 ° C.
• the element evaluation was performed in the same manner as in Example 2.
• Example 5 Compound (A-4) is synthesized according to scheme (15), and then polymer (P-4) is synthesized.
• Example 2 Polymerization and post-treatment were carried out in the same manner as in Example 1 except that 2.5 g of compound (A-4), 10 ml of dehydrated toluene, 34.1 mg of AIBN as a catalyst, and polymerization time were changed to 20 hours. 4) 1.21 g was obtained.
• the polymer had a Mw of 13,000 and a molecular weight distribution of 2.1.
• the Tg of the polymer was 262 ° C.
• the element evaluation was performed in the same manner as in Example 2.
• Example 6 Compound (A-5) is synthesized according to scheme (16), and then polymer (P-5) is synthesized.
• a white powder was obtained by carrying out the reaction and post-treatment in the same manner as in Example 5 except that 8.8 g (38.3 mmol) of 4-iodobenzaldehyde was used for 6.4 g (19.3 mmol) of compound (A-1). 3.2 g (yield 71%) of compound (A-5) was obtained.
• Example 2 Polymer and polymerization were conducted in the same manner as in Example 1 except that 2.0 g of compound (A-5), 20 ml of dehydrated toluene, 25.6 mg of AIBN as a catalyst were added, and the polymerization time was changed to 28 hours. 1.13 g of (P-5) was obtained. The polymer had a Mw of 11,000 and a molecular weight distribution of 1.9. The polymer Tg was 275 ° C. The element evaluation was performed in the same manner as in Example 2.
• Example 7 Compound (A-7) is synthesized according to scheme (17), and then polymer (P-6) is synthesized.
• a mixed solution containing 1.2 g of compound (A-7) and 1 ml of ethylbenzene in a 25 ml eggplant type flask was devolatilized and repeatedly purged with nitrogen, and then polymerized at a bath temperature of 125 ° C. for 65 hours.
• the polymerization solution was diluted and purified by reprecipitation using methanol.
• the purified polymer content was recovered, and this was again put into methanol and repeatedly reslurried to obtain 0.54 g of polymer (P-6).
• This polymer had Mw of 300,000 and a molecular weight distribution of 2.3.
• the polymer Tg was 280 ° C.
• the element evaluation was performed in the same manner as in Example 2.
• Example 2 Polymerization and post-treatment were performed in the same manner as in Example 1 except that the compound (B-6) was used as the soot monomer.
• the obtained polymer (EP-1) had Mw of 29,000 and a molecular weight distribution of 2.3.
• the Tg of the polymer was 137 ° C.
• the element evaluation was performed in the same manner as in Example 2.
• Example 2 Polymerization and post-treatment were performed in the same manner as in Example 1 except that 4- (N-carbazyl) methylstyrene was used as the monomer.
• the obtained 4- (N-carbazyl) methylstyrene polymer (polymer (EP-2)) had an Mw of 11,000 and a molecular weight distribution of 2.0.
• the Tg of the polymer was 148 ° C.
• the element evaluation was performed in the same manner as in Example 2.
• Table 1 shows the polymers used for device evaluation and the evaluation results. All the polymers were used for the hole transport layer. The luminance shown in Table 1 is a value at 20 mA / cm 2 . The maximum wavelength of the device emission spectrum was 550 nm, and green emission derived from an iridium complex was observed.
• Example 8 The compound (A-2) and the compound (B-6) obtained in Synthesis Example 6 were copolymerized to synthesize a copolymer (CP-1). Specifically, as shown in Scheme (19), 0.36 g (1.0 mmol) of compound (A-2) and 0.07 g (0.25 mmol) of compound (B-6) were dissolved in 20 ml of benzene, AIBN (4.7 mg) was added, and the reaction was carried out at 70 ° C. for 16 hours after nitrogen substitution. The reaction solution was diluted and purified by reprecipitation using acetonitrile. The purified polymer content was recovered, and this was again put into acetonitrile and repeatedly reslurried to obtain 0.14 g of polymer (CP-1).
• the resulting polymer was identified by GPC, TGA and DSC. Mw was 9,000 in terms of polystyrene of GPC (THF), and the molecular weight distribution was 2.2.
• Mw was 9,000 in terms of polystyrene of GPC (THF), and the molecular weight distribution was 2.2.
• required from DSC was 193 degreeC.
• Example 9 The device evaluation of the polymer (CP-1) obtained in Example 8 was carried out by first using a glass substrate with ITO having a film thickness of 150 nm that had been subjected to solvent washing and UV ozone treatment, and poly (3,4-ethylenediethylene as a hole injection layer.
• the synthesized polymer (CP-1) was dissolved in tetrahydrofuran to prepare a 0.4 wt% solution, and a film having a thickness of 20 nm was formed as a hole transport layer by spin coating.
• a vacuum deposition apparatus tris (2- (p-tolyl) pyridine) iridium (III) as a light emitting layer dopant and 4,4′-bis (9H-carbazol-9-yl) as a light emitting layer host Biphenyl was co-deposited so that the dopant concentration was 0.6 wt%, and a 40 nm film was formed as the light emitting layer.
• Alq 3 was formed to a thickness of 25 nm
• LiF / Al was formed to a thickness of 170 nm as a cathode
• this element was sealed in a glove box to produce an organic electroluminescent element.
• the organic electroluminescence device When an external power source was connected to the organic electroluminescence device thus obtained and a DC voltage of 0 to 10 V was applied, it was confirmed that the organic EL device had the light emission characteristics as shown in Table 2 at a current density of 20 mA / cm 2 .
• the maximum wavelength of the device emission spectrum was 550 nm, and green emission derived from an iridium complex was observed.
• Example 10 A copolymer (CP-2) was obtained in the same manner as in Example 8 except that the amount of AIBN as an initiator was changed to 2.0 mg. This polymer had Mw of 24,000, molecular weight distribution of 2.3, (A-2) / (B-6) of 72/28 (mol / mol), and Tg of 194 ° C. The element evaluation was performed in the same manner as in Example 9.
• Example 11 A polymer (CP-3) is synthesized according to scheme (20).
• AIBN was added as a catalyst to a mixture of 0.45 g (1.0 mmol) of compound (A-3), 0.03 g (0.11 mmol) of compound (B-6) and 20 ml of dehydrated THF in a 50 ml eggplant-shaped flask. After 5.0 mg was added and devolatilization and nitrogen substitution were repeated, polymerization was carried out at 60 ° C. for 24 hours. After the polymerization solution was diluted, it was purified by reprecipitation using acetone. The purified polymer content was recovered, and this was put into acetone again and repeatedly reslurried to obtain 0.14 g of copolymer (CP-3).
• This polymer had Mw of 21,000, molecular weight distribution of 2.3, Tg of 204 ° C., and (A-3) / (B-6) of 84/16 (mol / mol).
• the device evaluation of the obtained copolymer (CP-3) was carried out in the same manner as in Example 9.
• Table 2 shows the polymers used for device evaluation and the evaluation results. All the polymers were used for the hole transport layer.
• the hole injection property of the organic electroluminescence device is improved and the light emission efficiency is excellent.
• a large-area element can be easily manufactured by a coating film forming method or the like.

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